Water-insoluble monoazo-dyestuffs



United States Patent Ofiice 3,342,803 Patented Sept. 19, 1967 3,342,803WATER-INSOLUBLE MONOAZO-DYESTUFFS Klaus Artz, Muttenz, and Paul Rhyner,Basel, Switzerland,

assignors to Ciba Limited, Basel, Switzerland, a Swiss company NoDrawing. Filed Jan. 23, 1964, Ser. No. 339,817 Claims priority,application Switzerland, Feb. 21, 1963, 2,204/ 63 6 Claims. (Cl.260-207) The present invention provides new, valuable waterinsolublemonoazo dyestuflfs of the formula R1 NHCOR3 in which R represents ahydrogen or a halogen atom or an alkoxy, alkyl or trifluoromethyl group,R represents a hydrogen or a halogen atom or an alkyl, trifluoromethylor alkoxy group, R represents a hydrogen atom or an alkyl, alkoxy orcycloalkyl group that may be substituted.

or a benzene radical that may be substituted, R represents a hydrogenatom or an alkyl or alkoxy group, and R represents a cyanoalkoxyalkylgroup or an acyloxyalkyl group.

The new dyestuflis are obtained when a diazo compound of an amine of theformula in which formulae R R R R and R have the meanings given above.

The following amines are examples of suitable diazo components:

2: 4-dinitro aniline,

2:4-dinitro-6-chloroor bromo-aniline, 2:4-dinitro-6-methylaniline,2:4-dinitro-3 6-dichloraniline, and2:4-dinitro-3-trifluoromethyl-6-chloraniline.

In the amines of the Formula 3 to be used as coupling components, R mayrepresent an alkyl or alkoxy group, for example, a methyl, ethyl,propyl, butyl or cyclohexyl group or a substituted alkyl group, as, forexample, a

chloromethyl, a methoxymethyl or an unsaturated alkyl group such as avinyl or a propylene group. R may also represent a hydrogen atom or analkoxy group, for example, a methoxy, ethoxy or ,B-chlorethoxy group. R

advantageously represents a cyanoethoxyalkyl group, in

1y an aliphatic acyloxyalkyl group, for example, an acetoxyethyl, apropionoxyethyl group or a butyryloxyethyl group. For example, R mayrepresent the following:

-OH2CH2OGH2CH2CN CHzCH-CHOOH2CHCN, CH:CHCH2OCHgCH;ON,

( J1 OCHaCHzCN OH2OHzOC0GHa, -CHgOHzOCOCHzCH;, -oH2oH,ooooHzoH2oH= Thefollowing are examples of coupling components:

OICHz NHCHQCHIO CHzCHzCN,

l NHC OCH:

OCH;

NHCHaCHzOCHaCN NBC 0 CH3 OCzH NHCHECHZOCHzCHZCN, NHCHCH2OCOCH:

I NHCHO NHCOCH:

NH0 0 O CzH's NHCHzCHgOCHzCHzCN NHCOCHzCHaacid, and sodium nitrite or,for example with a solution of nitrosylsulfuric acid in concentratedsulfuric acid.

The coupling operation may also be carried out by known methods, forexample, in a neutral to acid medium, if desired or required, in thepresence of sodium acetate 'or similar buffers or catalysts thatinfluence the rate of coupling, for example, pyridine or salts thereof.

When the coupling reaction is finished, the dyestuffs formed can beisolated from the coupling mixture, for example, by filtration becausethey are virtually insoluble in water.

Instead of a single diazo component, a mixture of two or more of thediazo components of the invention may be used and, instead of a singlecoupling component, a mixture of two or more of the coupling componentsthe invention may also be used, or a mixture comprising one of the saidcoupling components and a bis-(cynaoalkoxya1kyl)-ani1ine or abis-(acyloxyalkyl)-aniline, for example, a mixture of amines of theformulae (4) NH-CHzCHzO CHaCN NHCO Ra CH CHgO CHgCHzCN N lCHzCHzOCHzCHaCN NHCOR:

A-fter conversion into a finely dispersed form, the new monoazodyestuffs are eminently suitable for dyeing synthetic fibers, especiallyfibers made of aromatic polyesters. Deep reddish blue to greenish bluedyeings are obtained that exhibit a good fastness to light andsublimation. The new dyestuffs also reserve well on wool.

The new dyestuffs can also be used with advantage in admixture withother dyestuffs, especially with dyestuffs of the formula Iii: N01 R4 RxNHCOR:

in which R R R and R have the meanings given above, and Y represents abis-(cyanoalkoxyalkyl)-amino group or a bis-(acyloxyalkyl) -amino group.

Compared with the dyestuffs described in French specification No.1,261,580, the dyestuffs obtained by the process of the invention aredistinguished 'by better properties of fastness. Moreover, they showgood affinity for polyester fibers when applied from an alkaline bath,and they reserve wool better.

The following examples illustrate the invention. Unless otherwisestated, the parts and percentages are by weight.

Example 1 1.8 parts of 2:4-dinitroaniline was introduced, at to 5 0.,into 20 parts of concentrated sulfuric acid in which 0.7 part of sodiumnitrite had been dissolved, the whole was stirred at that temperaturefor 1 hour and then discharged on to ice. 2.8 parts of2-methoxy-5-acetylamino- N-(B-cyanoethoxylethyl)-aniline, dissolved in100 parts of 2 N hydrochloric acid, were poured into the solution. Thedyestuff of the formula was precipitated by the addition of saturatedsodium acetate solution and then isolated by suction filtration. Thedyestuff thus obtained yielded blue dyeings possessing good propertiesof fasteness when applied to polyester fibers in the form of an aqueousdispersion.

The above-mentioned coupling component was obtained by additivelycombining acrylonitrile withZ-methoxy-S-acetamide-N-(hydroxyethyl)-aniline in the presence of abase, or by reacting Z-methoxy-S-acetylaminoaniline with 1 mol ofB-chlorethyl-B-cyanoethyl ether.

The dyestuff obtained as described in the first paragraph could also beused with advantage in admixture with one of the following dyestuffs,for example, in a ratio of '1: l:

NHCO OH:

NO: 0 CH3 CaH40 C2H4CN ON N=N N 021140 CzHiCN NHCO CH3 NO: 0 CH:

/C:H OH OaN N: N

| NHCOCH;

Blue dyeings possessing good properties of fastness were likewiseobtained on polyester fibers.

Example 2 2:2 parts of 2:-dinitro-6-chloroaniline were introduced, at 0to 5 C., into 20 parts of concentrated sulfuric acid in which 0.7 partof sodium nitrite had been dissolved, the whole was stirred at thattemperature for 1 hour and then discharged on to ice. 2. parts of2-methoxy-5-acetylamino-N-(/3-cyanoethoxyethyl)-aniline, dissolved inparts of 2 N hydrochloric acid, were poured into the solution. Thedyestuff of the formula was precipitated by the addition of saturatedsodium acetate solution and then isolated by suction filtration. Thedyestuff thus obtained yielded blue dyeings possessing good propertiesof fastness when applied to polyester fibers in the form of an aqueousdispersion.

By using 2.5 parts of 224-dinitro-6-bromoaniline instead of2:4-dinitro-6-chloroaniline, a dyestuff having very similar dyeingproperties was obtained.

The dyestulf obtained as described in the first paragraph may also beused with advantage in admixture with one of the following dyestuffs,for example, in a ratio of 1:1:

NHCOCH;

N01 0 CH3 OgNO-N=NN-(C:H4OC1H4CN)1 NHCOCH:

0111.011 OzN N: N

H NHCOCH:

N03 0 CH:

CzHrO C 0 CH3 Oa N=N N\ I 011140 0 0 CH3 NH0 0 CH3 Example 3 1.8 partsof 2:4-dinitroaniline were introduced, at 0 to 5 C., in 20 parts ofconcentrated sulfuric acid in which 0.7 part of sodium nitrite had beendissolved, the whole was stirred for 1 hour and then discharged on toice. 2.7 parts of Z-methoxy-S-acetylamino-N-(acetoxyethyl)- aniline,dissolved in 100 parts of 2 N hydrochloric acid, were poured into thesolution. The dyestuff of the formula N02 OCH3 CgH4O C 0 CH NHCOCHI wasprecipitated by the addition of saturated sodium acetate solution andthen isolated by suction filtration. The dyestuff thus obtained yieldedblue dyeings possessing good properties of fastness when applied topolyester fibers in the form of an aqueous dispersion.

3,342,803 6 The above-mentioned coupling components could be What isclaimed is: obtained by acylating 2-methoxy-5-acetylamino-N-(hy- 1. Amonoazo-dyestulf of the formula droxyethyl)-aniline or by reactingZ-methoxy-S-acetylaminoaniline with 1 mol of aceticacid-fl-chlorethylester.

The dyestuff obtained in the manner described in the 5 o, R, firstparagraph could also be used with advantage in admixture with one of thefollowing dyestutfs, for example, Q,N QN=N NHR; inaratiooflzl:

N0; OCH; R1 NHCOR| l 10 0|NN=N -NHCzH4O ozmoN in which R represents amember selected from the group NHCOOH, consisting of hydrogen, chlorine,bromine and lower alkyl. R represents lower alkyl, R; stands for amember selected mmoczmcN from the group consisting of hydrogen, loweralkyl and o N lower alkoxy and R represents a member selected from T thegroup consisting of cyanoethoxyethyl and ethyl lower- 0111400134alkanoyloxy-ethyl.

NHCO 2. A monoazo dyestulf of the formula No, OCH;

/C H O 0 0 CH;

0,1140 0 0 CH: NBC 0 0H; 0,N N=N NHCHiCHlOCHiCHflCN Blue dyeingspossessing good properties of fastness were likewise obtained onpolyester fibers. R1 NHCOR' The following table contains furtherdyestuffs characterized by the substituents R R R R and R as abovedefined and which were prepared in a manner analogous in which Rrepresents a member selected from the group 1 part of an aqueous pasteof the dyestufi obtained as from the group consisting of hydrogen, loweralkyl and described in Example 1 and approximately 1 part of dried lowerY- sulfite cellulose waste liquor were ground in a roller mill 3. Thedyestulf of the formula to form a fine paste having a dyestuif contentof approximately 10%. o

taining 1 to 2 parts of the sodium salt ofN-benzylheptadecyl-benzimidazole disulfonic acid and 1 part ofconcentrated aqueous ammonia solution per 1000 parts of water. Thematerial was then entered into a dyebath com- N03 100 parts of fibrousmaterial made of polyethylene ter- I ephthalate were washed for half anhour in a bath con- N=N QNHCHCH=OCH1CHQCN 31 gIHCOCaOH;

4. The dyestufi of the formula prising 3000 parts of water to which 1.5parts by volume of 80% acetic acid had been added and in which 10 lparts of the dyestutf paste obtained as described in the OZNO N=NQNHOHIOEOOHCHCN first paragraph had been dispersed in the presence of 54parts of the sodium salt of N-benzyl- -heptadecyl benzim- NHCOGHCH3idazole disulfonic acid. The whole was heated to 130 C.

in a pressure vessel and kept at that temperature for 1 5. The dyestuflof the formula hour. The material was then well rinsed and, if desiredor required, washed for half an hour at 60 to 80 c. with OOHQ a solutioncontaining 1 part of the sodium salt of N- benzyl- -heptadecylbenzimidazole disulfonic acid for O NHCH"CHOCH'CHCN 1000 parts of water.A blue dyeing possessing good properties of fastness was obtained. OC

3,342,803 7 8 6. The dyestuff of the formula References Cited UNITEDSTATES PATENTS 3,178,405 4/1965 Merian 260-207 5 FOREIGN PATENTS 856,34812/1960 Great Britain.

NHCHNHWCHNHZCN CHARLES B. PARKER, Primary Examiner.-

NHCO cmcmcg, 10 F. D. HIGEL, Assistant Examiner.

UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION Patent No.3,342,803 September 19, 1967 Klaus Artz et a1.

It is hereby certified that error appears in the above numbered patentrequiring correction and that the said Letters Patent should read ascorrected below.

Column 6, lines 56 to 60, for that portion of the formula readingNHCOC2CH3 read NHCOCHZCH3 Signed and sealed this 21st day of January1969.

(SEAL) Attest:

EDWARD J. BRENNER Commissioner of Patents Edward M. Fletcher, Jr.

Attesting Officer

1. A MONOAZO-DYESTUFF OF THE FORMULA